WO2022064549A1 - 半導体装置の製造方法、記録媒体及び基板処理装置 - Google Patents
半導体装置の製造方法、記録媒体及び基板処理装置 Download PDFInfo
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- WO2022064549A1 WO2022064549A1 PCT/JP2020/035708 JP2020035708W WO2022064549A1 WO 2022064549 A1 WO2022064549 A1 WO 2022064549A1 JP 2020035708 W JP2020035708 W JP 2020035708W WO 2022064549 A1 WO2022064549 A1 WO 2022064549A1
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- substrate
- gas
- molybdenum
- semiconductor device
- film
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- 239000000758 substrate Substances 0.000 title claims abstract description 69
- 239000004065 semiconductor Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000007789 gas Substances 0.000 claims description 158
- 238000000034 method Methods 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 26
- 239000011733 molybdenum Substances 0.000 claims description 26
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000032258 transport Effects 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000003746 surface roughness Effects 0.000 abstract description 21
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 235000012431 wafers Nutrition 0.000 description 84
- 239000011261 inert gas Substances 0.000 description 25
- 238000003860 storage Methods 0.000 description 12
- 230000007246 mechanism Effects 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003779 heat-resistant material Substances 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000003254 palate Anatomy 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28079—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a single metal, e.g. Ta, W, Mo, Al
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28568—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising transition metals
Definitions
- the present disclosure relates to a method for manufacturing a semiconductor device, a recording medium, and a substrate processing device.
- a low resistance tungsten (W) film is used as a word line of a NAND flash memory or DRAM having a three-dimensional structure.
- a titanium nitride (TiN) film may be used as a barrier film between the W film and the insulating film (see, for example, Patent Document 1 and Patent Document 2).
- a molybdenum (Mo) film containing molybdenum (Mo) is used to reduce the thickness and resistance.
- the Mo film has a large surface roughness (surface roughness), and it is an issue to improve the embedding performance of the Mo film. Further, when the Mo film is formed on the underlying metal film, the metal element may diffuse into the film from the underlying metal film.
- the object of the present disclosure is to provide a technique capable of suppressing diffusion from a substrate while improving the surface roughness of a molybdenum-containing film.
- A The process of accommodating the substrate in the processing container and (B) A step of heating the substrate to 445 ° C. or higher and 505 ° C. or lower, and (C) A step of supplying molybdenum-containing gas to the substrate and (D) A step of supplying a reducing gas to the substrate.
- E A technique for forming a molybdenum-containing film on the substrate is provided by performing (c) and (d) one or more times after (b).
- FIG. 1 is a schematic cross-sectional view taken along the line AA in FIG.
- FIG. 5A is a diagram showing a cross section of the substrate before forming the Mo-containing film on the substrate
- FIG. 5B shows a cross section of the substrate after forming the Mo-containing film on the substrate. It is a figure. It is a figure which showed the relationship between the average roughness (Ra) of the Mo-containing film formed in each of Samples 1 to 5, and the temperature of a substrate.
- FIGS. 1 to 5 explanation will be given with reference to FIGS. 1 to 5. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings do not always match the actual ones. Further, even between the plurality of drawings, the relationship of the dimensions of each element, the ratio of each element, and the like do not always match.
- the substrate processing device 10 includes a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system).
- the heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.
- an outer tube 203 constituting a reaction vessel (processing vessel) is arranged concentrically with the heater 207.
- the outer tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open.
- a manifold (inlet flange) 209 is arranged concentrically with the outer tube 203.
- the manifold 209 is made of a metal such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends.
- An O-ring 220a as a sealing member is provided between the upper end portion of the manifold 209 and the outer tube 203.
- an inner tube 204 constituting the reaction vessel is arranged inside the outer tube 203.
- the inner tube 204 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open.
- a processing container (reaction container) is mainly composed of an outer tube 203, an inner tube 204, and a manifold 209.
- a processing chamber 201 is formed in the hollow portion of the processing container (inside the inner tube 204).
- the gas supply pipes 310 and 320 are provided with mass flow controllers (MFCs) 312 and 322, which are flow control units (flow control units), in order from the upstream side. Further, the gas supply pipes 310 and 320 are provided with valves 314 and 324, which are on-off valves, respectively. Gas supply pipes 510 and 520 for supplying the inert gas are connected to the downstream sides of the valves 314 and 324 of the gas supply pipes 310 and 320, respectively. The gas supply pipes 510 and 520 are provided with MFC 512, 522, which is a flow rate controller (flow control unit), and valves 514, 524, which are on-off valves, in this order from the upstream side.
- MFCs mass flow controllers
- Nozzles 410 and 420 are connected and connected to the tips of the gas supply pipes 310 and 320, respectively.
- the nozzles 410 and 420 are configured as L-shaped nozzles, and their horizontal portions are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204.
- the vertical portions of the nozzles 410 and 420 are provided inside the channel-shaped (groove-shaped) spare chamber 201a formed so as to project outward in the radial direction of the inner tube 204 and extend in the vertical direction.
- In the reserve chamber 201a are provided upward along the inner wall of the inner tube 204 (upward in the arrangement direction of the wafer 200).
- a plurality of gas supply holes 410a and 420a of the nozzles 410 and 420 are provided at heights from the lower part to the upper part of the boat 217, which will be described later. Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410a and 420a of the nozzles 410 and 420 is supplied to the entire area of the wafer 200 accommodated from the lower part to the upper part of the boat 217.
- the nozzles 410 and 420 may be provided so as to extend from the lower region to the upper region of the processing chamber 201, but are preferably provided so as to extend to the vicinity of the ceiling of the boat 217.
- the reducing gas as the processing gas is supplied into the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420.
- nitrogen (N 2 ) gas is supplied as an inert gas into the processing chamber 201 via the MFC 512, 522, valves 514, 524, and nozzles 410, 420, respectively.
- N 2 gas is used as the inert gas.
- the inert gas for example, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenone, in addition to N 2 gas, will be described.
- a rare gas such as (Xe) gas may be used.
- the processing gas supply system is mainly composed of gas supply pipes 310, 320, MFC 312, 322, valves 314, 324, and nozzles 410, 420, but only the nozzles 410, 420 may be considered as the processing gas supply system.
- the treated gas supply system may be simply referred to as a gas supply system.
- the Mo-containing gas supply system is mainly composed of the gas supply pipe 310, the MFC 312, and the valve 314, but even if the nozzle 410 is included in the Mo-containing gas supply system, it may be considered. good.
- the reducing gas supply system is mainly composed of the gas supply pipe 320, the MFC 322, and the valve 324, but the nozzle 420 may be included in the reducing gas supply system. .. Further, the inert gas supply system is mainly composed of gas supply pipes 510, 520, MFC 512, 522, and valves 514, 524.
- nozzles 410 and 420 arranged in a spare chamber 201a in an annular vertically long space defined by an inner wall of an inner tube 204 and an end portion of a plurality of wafers 200 are provided. Gas is transported via. Then, gas is ejected into the inner tube 204 from a plurality of gas supply holes 410a and 420a provided at positions facing the wafers of the nozzles 410 and 420. More specifically, the gas supply hole 410a of the nozzle 410 and the gas supply hole 420a of the nozzle 420 eject the processing gas or the like in the direction parallel to the surface of the wafer 200.
- the exhaust holes 204a are provided at positions facing the plurality of wafers 200, and the gas supplied from the gas supply holes 410a and 420a to the vicinity of the wafer 200 in the processing chamber 201 flows in the horizontal direction. , Flows into the exhaust passage 206 through the exhaust hole 204a.
- the exhaust hole 204a is not limited to the case where it is configured as a slit-shaped through hole, and may be configured by a plurality of holes.
- the manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201.
- a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201
- an APC (Auto Pressure Controller) valve 243 and a vacuum pump as a vacuum exhaust device. 246 is connected.
- the APC valve 243 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 operating, and further, the valve with the vacuum pump 246 operating. By adjusting the opening degree, the pressure in the processing chamber 201 can be adjusted.
- the exhaust system is mainly composed of the exhaust hole 204a, the exhaust passage 206, the exhaust pipe 2311, the APC valve 243, and the pressure sensor 245.
- the vacuum pump 246 may be included in the exhaust system.
- a seal cap 219 is provided as a furnace palate body that can airtightly close the lower end opening of the manifold 209.
- the seal cap 219 is configured to abut on the lower end of the manifold 209 from the lower side in the vertical direction.
- the seal cap 219 is made of a metal such as SUS and is formed in a disk shape.
- An O-ring 220b as a sealing member that comes into contact with the lower end of the manifold 209 is provided on the upper surface of the seal cap 219.
- a rotation mechanism 267 for rotating the boat 217 accommodating the wafer 200 is installed on the opposite side of the processing chamber 201 in the seal cap 219.
- the boat 217 as a substrate support is configured to arrange a plurality of wafers, for example, 25 to 200 wafers 200, in a horizontal posture and at intervals in the vertical direction while being centered on each other. ..
- the boat 217 is made of a heat resistant material such as quartz or SiC.
- a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in a horizontal posture in multiple stages (not shown). With this configuration, the heat from the heater 207 is less likely to be transmitted to the seal cap 219 side.
- this embodiment is not limited to the above-mentioned embodiment.
- a heat insulating cylinder configured as a tubular member made of a heat-resistant material such as quartz or SiC may be provided.
- a temperature sensor 263 as a temperature detector is installed in the inner tube 204, and the amount of electricity supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263.
- the temperature in the processing chamber 201 is configured to have a desired temperature distribution.
- the temperature sensor 263 is L-shaped like the nozzles 410 and 420, and is provided along the inner wall of the inner tube 204.
- the controller 121 which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d.
- the RAM 121b, the storage device 121c, and the I / O port 121d are configured so that data can be exchanged with the CPU 121a via the internal bus.
- An input / output device 122 configured as, for example, a touch panel or the like is connected to the controller 121.
- the RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily held.
- the I / O port 121d includes the above-mentioned MFC 312,322,512,522, valve 314,324,514,524, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, and boat. It is connected to an elevator 115 or the like.
- the CPU 121a is configured to read a control program from the storage device 121c and execute it, and to read a recipe or the like from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like.
- the CPU 121a has an operation of adjusting the flow rate of various gases by the MFC 312, 322, 512, 522, an opening / closing operation of the valves 314, 324, 514, 524, an opening / closing operation of the APC valve 243, and an APC valve 243 so as to follow the contents of the read recipe.
- the controller 121 is stored in an external storage device (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or DVD, a magneto-optical disk such as MO, a semiconductor memory such as a USB memory or a memory card) 123.
- the above-mentioned program can be configured by installing it on a computer.
- the storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, these are collectively referred to simply as a recording medium.
- the recording medium may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them.
- the program may be provided to the computer by using a communication means such as the Internet or a dedicated line without using the external storage device 123.
- Substrate processing step As one step of the manufacturing process of the semiconductor device (device), an example of a step of forming a Mo-containing film containing molybdenum (Mo) used as a control gate electrode of, for example, 3D NAND on a wafer 200. , FIG. 4, FIG. 5 (A) and FIG. 5 (B) will be described.
- a metal-containing film containing aluminum (Al), which is a non-transition metal element is formed on the surface, and an aluminum oxide (AlO) film, which is a metal oxide film, is formed.
- AlO aluminum oxide
- a Mo-containing film is formed on the wafer 200 on which the AlO film is formed by the substrate processing step described later.
- the step of forming the Mo-containing film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operation of each part constituting the substrate processing device 10 is controlled by the controller 121.
- (A) A step of accommodating the wafer 200 in the processing chamber 201 inside the processing container, and (B) A step of heating the wafer 200 to 445 ° C or higher and 505 ° C or lower, and (C) A step of supplying the metal-containing gas to the wafer 200 and (D) A step of supplying a reducing gas to the wafer 200.
- the Mo-containing film is formed on the wafer 200 by performing (c) and (d) one or more times.
- wafer When the word “wafer” is used in the present specification, it may mean “wafer itself” or “a laminate of a wafer and a predetermined layer, film, etc. formed on the surface thereof". be.
- wafer surface When the term “wafer surface” is used in the present specification, it may mean “the surface of the wafer itself” or “the surface of a predetermined layer, film, etc. formed on the wafer”. be.
- the use of the term “wafer” in the present specification is also synonymous with the use of the term “wafer”.
- the inside of the processing chamber 201 that is, the space where the wafer 200 is present, is evacuated by the vacuum pump 246 so as to have a desired pressure (degree of vacuum).
- the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled based on the measured pressure information (pressure adjustment).
- the vacuum pump 246 is always kept in operation until at least the processing for the wafer 200 is completed.
- the inside of the processing chamber 201 is heated by the heater 207 so as to have a desired temperature.
- the amount of electricity supplied to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment).
- the temperature of the heater 207 is such that the temperature of the wafer 200 is, for example, a temperature in the range of 445 ° C. or higher and 505 ° C. or lower, preferably a temperature in the range of 445 ° C. or higher and 470 ° C. or lower. Set and do.
- the heating in the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed.
- Step S10 Metal-containing gas supply
- the valve 314 is opened to allow a metal-containing gas, which is a raw material gas, to flow into the gas supply pipe 310.
- the flow rate of the metal-containing gas is adjusted by the MFC 312, is supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410, and is exhausted from the exhaust pipe 231.
- the metal-containing gas is supplied to the wafer 200.
- the valve 514 is opened to allow an inert gas such as N 2 gas to flow into the gas supply pipe 510.
- the flow rate of the inert gas flowing in the gas supply pipe 510 is adjusted by the MFC 512, is supplied into the processing chamber 201 together with the metal-containing gas, and is exhausted from the exhaust pipe 231.
- the valve 524 is opened and the inert gas is allowed to flow into the gas supply pipe 520.
- the inert gas is supplied into the processing chamber 201 via the gas supply pipe 320 and the nozzle 420, and is exhausted from the exhaust pipe 231.
- the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 3990 Pa, for example, 1000 Pa.
- the supply flow rate of the metal-containing gas controlled by the MFC 312 is, for example, a flow rate in the range of 0.1 to 1.0 slm, preferably 0.1 to 0.5 slm.
- the supply flow rate of the inert gas controlled by the MFC 512 and 522 is, for example, a flow rate within the range of 0.1 to 20 slm.
- the notation of a numerical range such as "1 to 3990 Pa" in the present disclosure means that the lower limit value and the upper limit value are included in the range. Therefore, for example, "1 to 3990 Pa" means “1 Pa or more and 3990 Pa or less". The same applies to other numerical ranges.
- the only gases flowing in the processing chamber 201 are the metal-containing gas and the inert gas.
- the metal-containing gas a molybdenum (Mo) -containing gas containing molybdenum (Mo) and oxygen (O) can be used.
- Mo-containing gas for example, molybdenum dichloride (MoO 2 Cl 2 ) gas and molybdenum tetrachloride (MoOCl 4 ) gas can be used.
- MoO 2 Cl 2 molybdenum dichloride
- MoOCl 4 molybdenum tetrachloride
- the Mo-containing layer may be a Mo layer containing Cl or O, an adsorption layer of MoO 2 Cl 2 , or both of them.
- the Mo-containing layer is a film containing Mo as a main component and may contain elements such as Cl, O, and H in addition to the Mo element.
- the inside of the processing chamber 201 is purged.
- the valves 514 and 524 are left open to maintain the supply of the inert gas into the processing chamber 201.
- the inert gas acts as a purge gas, and can enhance the effect of removing the unreacted metal-containing gas remaining in the treatment chamber 201 or the metal-containing gas after contributing to the formation of the metal-containing layer from the treatment chamber 201.
- Step S12 (Reduction gas supply) After removing the residual gas in the processing chamber 201, the valve 324 is opened and the reducing gas is allowed to flow in the gas supply pipe 320. The flow rate of the reducing gas is adjusted by the MFC 322, the reducing gas is supplied into the processing chamber 201 through the gas supply hole 420a of the nozzle 420, and is exhausted from the exhaust pipe 231. At this time, the reducing gas is supplied to the wafer 200. At the same time, the valve 524 is opened to allow the inert gas to flow into the gas supply pipe 520. The flow rate of the inert gas flowing in the gas supply pipe 520 is adjusted by the MFC 522.
- the inert gas is supplied into the processing chamber 201 together with the reducing gas and is exhausted from the exhaust pipe 231.
- the valve 514 is opened and the inert gas is allowed to flow into the gas supply pipe 510.
- the inert gas is supplied into the processing chamber 201 via the gas supply pipe 310 and the nozzle 410, and is exhausted from the exhaust pipe 231.
- the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 3990 Pa, for example, 2000 Pa.
- the supply flow rate of the reducing gas controlled by the MFC 322 is, for example, a flow rate in the range of 1 to 50 slm, preferably 15 to 30 slm.
- the supply flow rate of the inert gas controlled by the MFC 512 and 522 is, for example, a flow rate within the range of 0.1 to 30 slm.
- the time for supplying the reducing gas to the wafer 200 is, for example, a time in the range of 0.01 to 120 seconds.
- the only gases flowing in the processing chamber 201 are the reducing gas and the inert gas.
- the reducing gas for example, hydrogen (H 2 ) gas, deuterium (D 2 ) gas, gas containing activated hydrogen and the like can be used.
- H 2 gas is used as the reducing gas
- the H 2 gas undergoes a substitution reaction with at least a part of the Mo-containing layer formed on the wafer 200 in step S10. That is, O and chlorine (Cl) in the Mo-containing layer react with H 2 and are desorbed from the Mo layer to react with water vapor (H 2 O), hydrogen chloride (HCl), chlorine (Cl 2 ) and the like. It is discharged from the processing chamber 201 as a product.
- a metal layer (Mo layer) containing Mo and substantially free of Cl and O is formed on the wafer 200.
- Step S13 (second purge step)] (Removal of residual gas)
- the valve 324 is closed to stop the supply of the reducing gas.
- the reducing gas and reaction by-products remaining in the treatment chamber 201 after contributing to the formation of the unreacted or metal layer are placed in the treatment chamber 201. Exclude from. That is, the inside of the processing chamber 201 is purged.
- a metal having a predetermined thickness (for example, 0.5 to 20.0 nm) is placed on the wafer 200. Form a containing film.
- the above cycle is preferably repeated multiple times. Further, each of the steps S10 to S13 may be performed at least once or more.
- Inert gas is supplied into the processing chamber 201 from each of the gas supply pipes 510 and 520, and is exhausted from the exhaust pipe 231.
- the inert gas acts as a purge gas, whereby the inside of the treatment chamber 201 is purged with the inert gas, and the gas and reaction by-products remaining in the treatment chamber 201 are removed from the inside of the treatment chamber 201 (after-purge).
- the atmosphere in the processing chamber 201 is replaced with the inert gas (replacement of the inert gas), and the pressure in the treatment chamber 201 is restored to the normal pressure (return to atmospheric pressure).
- the seal cap 219 is lowered by the boat elevator 115, and the lower end of the outer tube 203 is opened. Then, the processed wafer 200 is carried out (boat unloading) from the lower end of the outer tube 203 to the outside of the outer tube 203 in a state of being supported by the boat 217. After that, the processed wafer 200 is taken out from the boat 217 (wafer discharge).
- the wafer 200 is heated to a temperature in the range of 445 ° C. or higher and 505 ° C. or lower, preferably in the range of 445 ° C. or higher and 470 ° C. or lower, and then contains Mo.
- the MoO 2 Cl 2 gas which is a gas
- the H 2 gas which is a reducing gas
- the wafer 200 is in the range of 445 ° C. or higher and 470 ° C. or lower.
- the average roughness Ra of the surface roughness of the Mo-containing film formed by heating to the inside temperature is 0.8 nm or less.
- the average roughness Ra of the surface roughness of the Mo-containing film formed by heating the wafer 200 to a temperature within the range of 450 ° C. or higher and 465 ° C. or lower is 0.7 nm or less.
- the Mo-containing film formed by heating the temperature of the wafer 200 to a temperature lower than 445 ° C. has worse surface roughness as compared with the Mo-containing film formed by heating the temperature of the wafer 200 to 450 ° C. do.
- the Mo-containing film formed by heating the temperature of the wafer 200 to a temperature lower than 445 ° C. is a substrate in the film as compared with the Mo-containing film formed by heating the temperature of the wafer 200 to 450 ° C.
- the diffusion of Al from the AlO membrane is increased. This is because at a temperature lower than 445 ° C., the reduction by the H 2 gas becomes incomplete, the MoO 2 Cl 2 gas is not reduced, and MoO x Cly is produced. It is considered that this MoO x Cly causes the underlying AlO film and the formed Mo-containing film to be attacked.
- attack in the present disclosure means reduction.
- the Mo-containing film formed by heating the temperature of the wafer 200 to a temperature higher than 505 ° C. has a worse surface roughness as compared with the Mo-containing film formed by heating the temperature of the wafer 200 to 450 ° C. ..
- the Mo-containing film formed by heating the temperature of the wafer 200 to a temperature higher than 505 ° C. is a substrate in the film as compared with the Mo-containing film formed by heating the temperature of the wafer 200 to 450 ° C.
- the diffusion of Al from the AlO membrane is increased. It is considered that this is because the underlying AlO film and the formed Mo-containing film are attacked by the HCl produced as a reaction by-product at a temperature higher than 505 ° C.
- the average surface roughness is averaged.
- a Mo-containing film having a roughness Ra of 1.0 nm or less can be formed, and the surface roughness of the Mo-containing film can be improved. That is, it is possible to improve the embedding performance of the Mo-containing film used for the control gate electrode of 3D NAND. In addition, it is possible to suppress the diffusion of Al from the underlying AlO film into the Mo-containing film.
- FIG. 6 is a diagram showing the relationship between the surface roughness (average roughness Ra) of the Mo-containing films formed in Samples 1 to 5, respectively, and the temperature of the substrate.
- the surface of the Mo-containing film formed by heating the wafer of Sample 1 to 425 ° C and the wafer of Sample 5 are formed by heating to 550 ° C.
- the average roughness Ra of the surface of the Mo-containing film formed is larger than 1.0 nm, and the average roughness is larger than that of the surface of the Mo-containing film formed in Sample 2, Sample 3, and Sample 4, respectively, and the surface surface is large. It was confirmed that the roughness was bad.
- the average roughness Ra on the surface of the Mo-containing film formed by heating the wafer of No. 1 to 450 ° C. was 0.8 or less. That is, it was confirmed that the Mo-containing films formed on Sample 2, Sample 3, and Sample 4 each had a small average roughness and good surface roughness.
- the Mo-containing film is formed so that the temperature of the heater 207 in the substrate processing step described above is within the range of 445 ° C. or higher and 505 ° C. or lower for the wafer 200. It was confirmed that the surface roughness of the Mo-containing film was improved and the average roughness Ra of the surface roughness could be 1.0 nm or less. Further, the surface roughness of the Mo-containing film is formed by forming the Mo-containing film so that the temperature of the heater 207 in the substrate processing step described above is within the range of the temperature of the wafer 200 of 445 ° C. or higher and 470 ° C. or lower.
- the average roughness Ra of the surface roughness could be 0.8 nm or less.
- the surface roughness of the Mo-containing film is formed by forming the Mo-containing film so that the temperature of the heater 207 in the substrate processing step described above is within the range of 450 ° C. or higher and 465 ° C. or lower.
- the average roughness Ra of the surface roughness could be 0.7 nm or less.
- the Mo-containing film formed in Sample 2, Sample 3, and Sample 4 is suppressed from diffusing from the underlying AlO film, and in particular, the Mo-containing film formed in Sample 2 is Sample 3 and Sample 4. It was confirmed that the diffusion from the underlying AlO film was suppressed as compared with the Mo-containing film formed in each of the above.
- the temperature of the heater 207 in the substrate processing step described above is such that the temperature of the wafer 200 is in the range of 445 ° C. or higher and 505 ° C. or lower, preferably in the range of 445 ° C. or higher and 470 ° C. or lower. It was confirmed that the diffusion from the underlying AlO film was suppressed by forming the Mo-containing film.
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Abstract
Description
この課題を解決するために、上述したようなTiN膜とW膜を用いる代わりに、モリブデン(Mo)を含有したモリブデン(Mo)膜を用いて、薄膜化と低抵抗化を図っているが、Mo膜は、膜の表面の粗さ(表面ラフネス)が大きく、Mo膜の埋め込み性能を向上させることが課題となっている。また、下地金属膜上にMo膜を形成すると、膜中に下地金属膜から金属元素が拡散してしまう場合がある。
(a)基板を処理容器に収容する工程と、
(b)前記基板を445℃以上505℃以下に加熱する工程と、
(c)前記基板に対してモリブデン含有ガスを供給する工程と、
(d)前記基板に対して還元ガスを供給する工程と、を有し、
(e)(b)の後、(c)と(d)とを1回以上行うことにより、前記基板上にモリブデン含有膜を形成する
技術が提供される。
基板処理装置10は、加熱手段(加熱機構、加熱系)としてのヒータ207が設けられた処理炉202を備える。ヒータ207は円筒形状であり、保持板としてのヒータベース(図示せず)に支持されることにより垂直に据え付けられている。
半導体装置(デバイス)の製造工程の一工程として、ウエハ200上に、例えば3DNANDのコントロールゲート電極として用いられるモリブデン(Mo)を含有するMo含有膜を形成する工程の一例について、図4、図5(A)及び図5(B)を用いて説明する。ここでは、図5(A)に示すように、表面に、非遷移金属元素であるアルミニウム(Al)が含まれた金属含有膜であり、金属酸化膜である酸化アルミニウム(AlO)膜が形成されたウエハ200を用いる。そして、後述する基板処理工程により、図5(B)に示すように、AlO膜が形成されたウエハ200上にMo含有膜を形成する。Mo含有膜を形成する工程は、上述した基板処理装置10の処理炉202を用いて実行される。以下の説明において、基板処理装置10を構成する各部の動作はコントローラ121により制御される。
(a)ウエハ200を処理容器内である処理室201に収容する工程と、
(b)ウエハ200を445℃以上505℃以下に加熱する工程と、
(c)ウエハ200に対して金属含有ガスを供給する工程と、
(d)ウエハ200に対して還元ガスを供給する工程と、を有し、
(e)(b)の後、(c)と(d)とを1回以上行うことにより、ウエハ200上にMo含有膜を形成する。
複数枚のウエハ200がボート217に装填(ウエハチャージ)されると、図1に示されているように、複数枚のウエハ200を支持したボート217は、ボートエレベータ115によって持ち上げられて、処理室201内に搬入(ボートロード)され、処理容器に収容される。この状態で、シールキャップ219はOリング220を介してアウタチューブ203の下端開口を閉塞した状態となる。
処理室201内、すなわち、ウエハ200が存在する空間が所望の圧力(真空度)となるように真空ポンプ246によって真空排気される。この際、処理室201内の圧力は、圧力センサ245で測定され、この測定された圧力情報に基づき、APCバルブ243がフィードバック制御される(圧力調整)。真空ポンプ246は、少なくともウエハ200に対する処理が完了するまでの間は常時作動させた状態を維持する。
(金属含有ガス供給)
バルブ314を開き、ガス供給管310内に原料ガスである金属含有ガスを流す。金属含有ガスは、MFC312により流量調整され、ノズル410のガス供給孔410aから処理室201内に供給され、排気管231から排気される。このとき、ウエハ200に対して金属含有ガスが供給される。このとき同時にバルブ514を開き、ガス供給管510内にN2ガス等の不活性ガスを流す。ガス供給管510内を流れた不活性ガスは、MFC512により流量調整され、金属含有ガスと一緒に処理室201内に供給され、排気管231から排気される。このとき、ノズル420内への金属含有ガスの侵入を防止するために、バルブ524を開き、ガス供給管520内に不活性ガスを流す。不活性ガスは、ガス供給管320、ノズル420を介して処理室201内に供給され、排気管231から排気される。
(残留ガス除去)
金属含有ガスの供給を開始してから所定時間経過後であって例えば0.01~10秒後に、ガス供給管310のバルブ314を閉じて、金属含有ガスの供給を停止する。つまり、金属含有ガスをウエハ200に対して供給する時間は、例えば0.01~10秒の範囲内の時間とする。このとき排気管231のAPCバルブ243は開いたままとして、真空ポンプ246により処理室201内を真空排気し、処理室201内に残留する未反応もしくは金属含有層形成に寄与した後の金属含有ガスを処理室201内から排除する。すなわち、処理室201内をパージする。このときバルブ514,524は開いたままとして、不活性ガスの処理室201内への供給を維持する。不活性ガスはパージガスとして作用し、処理室201内に残留する未反応もしくは金属含有層形成に寄与した後の金属含有ガスを処理室201内から排除する効果を高めることができる。
(還元ガス供給)
処理室201内の残留ガスを除去した後、バルブ324を開き、ガス供給管320内に、還元ガスを流す。還元ガスは、MFC322により流量調整され、ノズル420のガス供給孔420aから処理室201内に供給され、排気管231から排気される。このときウエハ200に対して、還元ガスが供給される。このとき同時にバルブ524を開き、ガス供給管520内に不活性ガスを流す。ガス供給管520内を流れた不活性ガスは、MFC522により流量調整される。不活性ガスは還元ガスと一緒に処理室201内に供給され、排気管231から排気される。このとき、ノズル410内への還元ガスの侵入を防止するために、バルブ514を開き、ガス供給管510内に不活性ガスを流す。不活性ガスは、ガス供給管310、ノズル410を介して処理室201内に供給され、排気管231から排気される。
(残留ガス除去)
金属層を形成した後、バルブ324を閉じて、還元ガスの供給を停止する。
そして、上述したステップS11(第1パージ工程)と同様の処理手順により、処理室201内に残留する未反応もしくは金属層の形成に寄与した後の還元ガスや反応副生成物を処理室201内から排除する。すなわち、処理室201内をパージする。
上記したステップS10~ステップS13の工程を順に行うサイクルを1回以上(所定回数(n回))行うことにより、ウエハ200上に、所定の厚さ(例えば0.5~20.0nm)の金属含有膜を形成する。上述のサイクルは、複数回繰り返すのが好ましい。また、ステップS10~ステップS13の工程をそれぞれ少なくとも1回以上行ってもよい。
ガス供給管510,520のそれぞれから不活性ガスを処理室201内へ供給し、排気管231から排気する。不活性ガスはパージガスとして作用し、これにより処理室201内が不活性ガスでパージされ、処理室201内に残留するガスや反応副生成物が処理室201内から除去される(アフターパージ)。その後、処理室201内の雰囲気が不活性ガスに置換され(不活性ガス置換)、処理室201内の圧力が常圧に復帰される(大気圧復帰)。
その後、ボートエレベータ115によりシールキャップ219が下降されて、アウタチューブ203の下端が開口される。そして、処理済ウエハ200がボート217に支持された状態でアウタチューブ203の下端からアウタチューブ203の外部に搬出(ボートアンロード)される。その後、処理済のウエハ200は、ボート217より取り出される(ウエハディスチャージ)。
本実施形態によれば、以下に示す1つまたは複数の効果を得ることができる。
(a)Mo含有膜の表面ラフネスを改善することができる。
(b)平坦性を有するMo含有膜を形成することができ、被覆率を向上させることができる。すなわち、3DNANDのコントロールゲート電極に用いられるMo含有膜の埋め込み性能を向上させることができる。
(c)膜中への下地金属膜からの金属元素の拡散を抑制することができる。
(d)高密度なMo膜を形成することが可能となり、生産性が向上される。
以上、本開示の実施形態を具体的に説明した。しかしながら、本開示は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能である。
上述した基板処理装置10を用いて、表面にAlO膜が形成されたウエハ200のサンプル1~サンプル5を用意した。そして、サンプル1~サンプル5に対して、それぞれ上述した基板処理工程におけるヒータ207の温度を、ウエハ200の温度が425℃、450℃、475℃、500℃、550℃となるように加熱して上述したステップS10~ステップS13を所定回数行って、表面にAlO膜が形成されたウエハ上にMo含有膜を形成した。
121 コントローラ
200 ウエハ(基板)
201 処理室
Claims (16)
- (a)基板を処理容器に収容する工程と、
(b)前記基板を445℃以上505℃以下に加熱する工程と、
(c)前記基板に対してモリブデン含有ガスを供給する工程と、
(d)前記基板に対して還元ガスを供給する工程と、を有し、
(e)(b)の後、(c)と(d)とを1回以上行うことにより、前記基板上にモリブデン含有膜を形成する半導体装置の製造方法。 - 前記基板の表面には、金属含有膜が形成されている請求項1記載の半導体装置の製造方法。
- 前記金属含有膜は、金属酸化膜である請求項2記載の半導体装置の製造方法。
- 前記金属は、非遷移金属である請求項2又は3記載の半導体装置の製造方法。
- 前記金属は、アルミニウムである請求項2から4のいずれか一項に記載の半導体装置の製造方法。
- 前記金属含有膜は、酸化アルミニウム膜である請求項2から5のいずれか一項に記載の半導体装置の製造方法。
- 前記モリブデン含有ガスは、モリブデンと酸素を含むガスである請求項1から6のいずれか一項に記載の半導体装置の製造方法。
- 前記モリブデン含有ガスは、モリブデンと酸素と塩素を含むガスである請求項1から7のいずれか一項に記載の半導体装置の製造方法。
- 前記モリブデン含有ガスは、二酸化二塩化モリブデンガスである請求項7又は8記載の半導体装置の製造方法。
- (b)では、前記基板の温度を445℃以上470℃以下に加熱する請求項1から9のいずれか一項に記載の半導体装置の製造方法。
- (b)では、前記基板の温度を450℃以上465℃以下に加熱する請求項1から9のいずれか一項に記載の半導体装置の製造方法。
- (e)は、膜表面の平均粗さが、1.0nm以下の前記モリブデン含有膜を形成する請求項1から11のいずれか一項に記載の半導体装置の製造方法。
- (e)は、膜表面の平均粗さが、0.8nm以下の前記モリブデン含有膜を形成する請求項10記載の半導体装置の製造方法。
- (e)は、膜表面の平均粗さが、0.7nm以下の前記モリブデン含有膜を形成する請求項11記載の半導体装置の製造方法。
- (a)基板処理装置の処理容器に基板を収容する手順と、
(b)前記基板を445℃以上505℃以下に加熱する手順と、
(c)前記基板に対してモリブデン含有ガスを供給する手順と、
(d)前記基板に対して還元ガスを供給する手順と、を有し、
(e)(b)の後、(c)と(d)とを1回以上行うことにより、前記基板上にモリブデン含有膜を形成する処理をコンピュータにより前記基板処理装置に実行させるプログラムが記録されたコンピュータ読み取り可能な記録媒体。 - 処理容器と、
前記処理容器内に基板を搬送する搬送系と、
前記処理容器内を加熱する加熱系と、
前記処理容器内にモリブデン含有ガスを供給するモリブデン含有ガス供給系と、
前記処理容器内に還元ガスを供給する還元ガス供給系と、
前記処理容器内を排気する排気系と、
(a)前記基板を前記処理容器に収容する処理と、
(b)前記基板を445℃以上505℃以下に加熱する処理と、
(c)前記基板に対して前記モリブデン含有ガスを供給する処理と、
(d)前記基板に対して前記還元ガスを供給する処理と、を有し、
(e)(b)の後、(c)と(d)とを1回以上行うことにより、前記基板上にモリブデン含有膜を形成する処理を行わせるように、前記搬送系、前記加熱系、前記モリブデン含有ガス供給系、前記還元ガス供給系及び前記排気系を制御することが可能なように構成される制御部と、
を有する基板処理装置。
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